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Introduction

It would be difficult to imagine a world without plastics. Among the most versatile materials ever developed, plastics can be made to resemble and even replace such diverse materials as metal, wood, glass, china, stone, cloth, rubber, jewels, glue, cardboard, varnish, and leather. The word plastic comes from the Greek plastikos, meaning “moldable” or “formable.” When heated to a liquid or semisolid form, plastics can be molded into almost any desired shape; when cool they harden into a solid.

Many different types of plastics exist, with new ones being developed as research continues. Different plastics are used for different purposes, but most of them tend to be strong, durable, lightweight, and resistant to corrosion. They are often less expensive than other materials and can be made in a wide variety of colors.

Plastics also serve as good electrical or heating insulators. Their versatility, durability, and low cost make them ideal materials for wide use in industry and in craftwork. Also for the same reasons plastics have replaced metal, wood, glass, and other materials in many applications.

Many common, and not-so-common, plastic items produced by industry have found their way into nearly every line of business. For instance, plastics are frequently substituted for objects originally made of metal because of their light weight and resistance to rust. Many automobile parts, such as headlights, bumpers, and side panels, are made of plastic. Radio, television, and computer cabinets can be molded entirely of plastic. Protective helmets of all sorts—football, baseball, construction, and even combat helmets—are made of plastic. The light weight and strength of plastics have made them essential to the aerospace industry.

Glasslike plastics are made into lenses, reflectors, costume jewelry, dentures, artificial eyes, soft-drink bottles and milk bottles, decorative murals, and moving parts in appliances, automobiles, and business machines. Plastic resins are used to make waterproof bags, wool that will not shrink, and collars that stay starched.

Plastics also can be made into disposable diapers; plates, cups, eating utensils, and nonstick cookware; coatings and adhesives; construction products; and clothing. Polystyrene, a snowlike foamed plastic, is popular not only with manufacturers but also with handicrafters for making novel, decorative items. The list is a long one, and new uses are found for plastics, it seems, day by day.

Development of Synthetic Plastics

Centuries before the first synthetic plastics were made, several naturally occurring substances were used as plastic material. These materials include gutta-percha, shellac, and the horns of animals. Gutta-percha is made from the sap of certain trees. Shellac is made from the secretions of a tiny scale insect. Before horn can be used it must be “plasticized,” or softened, by being boiled in water or soaked in an alkaline solution.

The first synthetic plastic was made from the plant material cellulose. In 1869 John Wesley Hyatt, an American printer and inventor, found that cellulose nitrate could be used as an inexpensive substitute for ivory. The mixture could be plasticized with the addition of camphor. Celluloid, as this new material was called, became the only plastic of commercial importance for some 30 years. It was used for eyeglass frames, combs, billiard balls, shirt collars, buttons, dentures, and photographic film. Just before the beginning of the 20th century, casein plastics were produced in France and Germany. Casein—milk protein—was treated with formaldehyde to produce the plastic material. Although still used today by button-makers, casein plastics otherwise have little importance.

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In 1909 Leo H. Baekeland, a Belgian-American chemist, developed phenol-formaldehyde, the first plastic made entirely from synthetic materials. Baekeland named the new material after himself, calling it Bakelite. Phenolic plastics such as Bakelite were used in construction components, wiring devices, automotive transmissions and power brakes, telephone relay systems, and electrical switch gear.

Baekeland’s development of Bakelite marked the true beginning of the plastics industry. Demand for the materials grew rapidly in the period from the late 1920s through World War II. During that time, many of the most important plastics entered into commercial production. These included polyvinyl chloride, the key member of the vinyl plastics family; low-density polyethylene, now the most widely used plastic, particularly in packaging; acrylics, which can be made as clear as glass; polystyrene, an exceptionally versatile plastic; and nylon, an extremely tough and durable material originally developed as a fiber substitute. The manufacture of synthetic rubbers, called elastomers, is often considered part of the plastics industry.

Composition

Most plastics are now made from the breakdown products of petroleum and coal. Petroleum has become the major source material for plastics.

Molecular Composition

All natural and synthetic plastics are organic compounds, because they contain the element carbon. Atoms of carbon can join together, much like a chain, to form a “backbone” for an extremely long molecule. These long-chain molecules are called polymers, from the Greek words poly, meaning “many,” and meros, meaning “part.”

A polymer consists of a large number of simpler molecules repeated over and over again in the chain. Each of these simpler molecules is called a monomer (“one part”). Monomers are chemically combined, or polymerized, to form a polymer chain. For example, many propylene monomers are combined to form polypropylene. (The names of many, but not all, plastics begin with the prefix poly. This indicates that plastics are polymeric materials.) When two or more different monomers are combined, the resulting polymer is called a copolymer.

Polymer chemists know that the properties of a plastic material are greatly influenced by the shape and chemical makeup of the polymer molecule. In their research, these scientists may try to change the characteristics of a polymer chain or devise new polymers to create plastics with certain desirable properties. Resistance to heat, toughness, and flexibility are among the properties that may be affected by changes in a plastic’s polymer molecule.

Resins and other ingredients

The words resin and plastic are often used as synonyms, but there is a difference. Resin is the raw, unfinished material; plastic is the material of the finished item. Resins can be made in various forms, including syrup, powder, flakes, or pellets.

Although resins may be used by themselves to produce plastic objects, more frequently other ingredients are added to form a compound. These other ingredients, generally called additives, may assist in the molding of the plastic object or add important properties to the finished product. Commonly used additives include fillers and reinforcing agents, plasticizers, stabilizers, colorants, flame retardants and smoke suppressants, and processing aids.

Fillers are inexpensive materials that are added to resins primarily to reduce costs. Some fillers are used only to extend the resins but many others also improve the properties of finished plastic products. Nonmetallic minerals are the most commonly used fillers. Of these, calcium carbonate is the most popular, especially for polyvinyl chloride. Other fillers include kaolin (a type of clay), talc, and mica. Fibrous additives, particularly fiberglass, are considered the most effective reinforcing agents. When added to plastics, fibrous reinforcements may improve a product’s rigidity, strength, and resistance to impact and cracking. Other fibrous additives include carbon fiber, aramid fiber (a type of nylon), and combinations called hybrids, such as aramid and carbon or aramid and glass. Plastics that contain reinforcements such as these are often called composites.

Plasticizers are added to resins to make them flow into molds more readily and, in some cases, to make them more flexible. Polyvinyl chloride, for example, is too hard and rigid to be useful unless plasticizers are added. Plasticizers work at the molecular level by loosening the polymer chains, which softens the polymer. Commonly used plasticizers are chemicals called phthalates, epoxidized oils, and phosphates.

Stabilizers prevent polymers from degrading, or breaking down. Heat stabilizers prevent degradation caused by the heat of processing. Since exposure to oxygen or ultraviolet radiation can also cause polymer degradation, antioxidants and ultraviolet light absorbers are also useful as stabilizers.

Colorants are added to plastics so that the finished product will be colored throughout. Plastics have an advantage over wood or metal, which can be colored only on the surface by means of paints or coatings. Dyes and pigments are used as colorants for plastics. Examples of colorants include titanium dioxide (by far the most common), iron oxides, and carbon black.

Flame retardants and smoke suppressants make plastics less flammable and toxic in case of fire. They are especially important for plastics used in appliances, carpets, furniture, aircraft, automobiles, electrical wiring, and construction materials. Adding flame retardants and smoke suppressants to plastics sometimes reduces other desirable properties. Aluminum trihydrate is the most common flame retardant.

Processing aids are additives that assist in the production of plastics. Lubricants, for example, improve the flow of resins in processing. Coupling agents help create stronger bonds between molecules.

Thermosets and Thermoplastics

Most plastics are described as being either thermosetting or thermoplastic. These terms refer to the reaction of a plastic to heat (thermo is Greek for “heat”).

Thermosetting plastics soften with heat but stay soft only for a short time. They set, or harden, if the heat continues. This process of making thermosetting plastics hard is called curing, which can also be accomplished by chemical means. In curing, the molecules of the plastic link together between chains (cross-link). Once these cross-links are formed, the plastic is no longer soft nor can it be resoftened through heating.

Thermoplastic materials also soften with heat but remain soft if the heat continues. They set only when cool and can be softened many times by reheating. In thermoplastics, the molecular chains do not cross-link during manufacture.

Manufacturers choose thermosetting plastics for objects that must withstand heat. Products made of these plastics can be subjected to very high temperatures—up to 500° F (260° C)—before they begin to char. Phenolics are the most commonly used thermosets. Others include epoxy resins, thermosetting polyester, and polyurethanes. Altogether, thermosets account for less than 15 percent of plastics production.

Thermoplastics are used for articles that are not subjected to unusual temperature changes. These plastics may soften or even melt at temperatures near 200° F (93° C). Most plastics production is of thermoplastics. These plastics include ABS (acrylonitrile-butadiene-styrene), acetals, acrylics, cellulosics, fluoropolymers, nylons, polycarbonate, thermoplastic polyester, polyethylene, polyethylene terephthalate, polypropylene, polystyrene, and polyvinyl chloride.

Manufacture

Extrusion molding is the predominant plastics-forming process used in industry today. In extrusion a heated thermoplastic compound is forced continuously through a forming die made in the desired shape. The process may be compared to squeezing toothpaste from a tube, in that it produces a long, usually narrow, continuous product. The formed plastic cools—under blown air or in a water bath—and hardens on a moving belt. Rods, tubes, pipes, and sheet and thin film (such as food wraps) are extruded, then coiled or cut to desired lengths. Plastic fibers are also made by an extrusion process. Liquid resin is squeezed through thousands of tiny holes called spinnerets to produce the fine threads from which acetate, nylon, rayon, and other plastic fabrics are woven.

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Injection molding, the second most widely used process, is employed for molding thermoplastics and some thermosetting materials. The plastic compound, heated to a semifluid state, is squirted into a mold under great pressure and hardens quickly. The mold then opens, and the part is released. The process can be repeated as many times as necessary and is particularly suited to mass production methods. Injection molding is used for a wide variety of plastic products, from small cups and toys to large objects weighing 30 pounds (14 kilograms) or more.

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In blow molding, air pressure is used to form hollow objects from thermoplastics. Manufacturers can use a direct or an indirect method of blow molding. In the direct method, a partially shaped, heated plastic form, called a parison, is inserted into a mold. Air is blown into the parison, forcing it to expand to the shape of the mold. In the indirect method of blow molding, a plastic sheet or special shape is heated, then clamped between a die and a cover. Air is forced between the plastic and the cover and presses the material into the shape of the die.

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Compression molding combines a thermosetting resin with a filler to create a molding compound. The compound is placed in a mold, the pieces of which are properly aligned by guide pins. Mechanical pressure is exerted on the mold, and the compound is heated to about 350° F (177° C). As the compound becomes semifluid, it is forced into every part of the mold. The plastic is allowed to cool and harden into a finished molded piece. Compression-molded products include telephone handsets, handles for pots and pans, and appliance and automotive parts.

Transfer molding, which combines compression and injection molding, is used most often for thermosetting plastics. As in injection molding, the plastic is heated in a chamber, then transferred into a mold by means of a plunger or ram. The process is similar to compression molding, because the plastic is cured in a mold under heat and pressure. Transfer molding is used to produce intricately shaped parts that may have deep holes or metal inserts.

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In thermoforming, a thermoplastic sheet is softened by heat and then placed over a mold. The sheet is made to conform to the mold by any of several methods and cools in the shape of the mold. Packaging of various types is made by thermoforming, as are parts for furniture, appliances, aircraft, and automobiles and recreational vehicles.

In casting, fluid resins are poured into open or closed molds, and little or no pressure is applied. Both thermosetting and thermoplastic materials can be cast. Cast thermoplastic films are used for packaging and photographic film; cast sheeting made of acrylic is used for glazing, skylights, windshields, and similar products. Rods and tubes may also be cast.

Calendering produces film and sheeting from thermoplastics by squeezing the plastic between heated rollers. Floor products, such as tiles made of polyvinyl chloride, are produced by calendering. This process can be used to apply plastic coatings to textiles.

Low-pressure molding, or reinforcing, uses resins that can be formed and cured with little or no heat and little or no pressure. This method makes it possible to mold irregularly shaped objects that are too large to mold in presses. Glass fiber, fabrics, paper, and wood veneer are impregnated (soaked) with resin and then laid on forms. Limited pressure, if needed, can be applied, and the assembly is cured with little or no heat. Hulls for small boats, fuselage sections for airplanes, and air ducts are formed in this manner.

High-pressure laminating combines layers of paper, cloth, or wood veneer. The layers are soaked with thermosetting resins and then bonded into flat sheets between the heated platens of a hydraulic press. Laminated materials are very strong. They are used indoors for tabletops and for wall panels and outdoors as waterproof plywood. They are also used in electrical and electronic products, aircraft and aerospace products, and in other products where high strength is necessary.

Reaction injection molding (RIM) is a relatively new process for producing objects made of thermosetting plastics, frequently polyurethanes. In RIM, liquid components are allowed to react (combine chemically) before they are injected into a mold and cured. Parts made by RIM are widely used in the automotive industry.

Foam molding also has become more widespread. Foamed plastics are expanded materials of cellular structure; they can be produced by any of several processes. Blowing agents can be added to either thermosetting or thermoplastic resins to produce foamed objects. Egg cartons and cups made of polystyrene foam are common examples of this type of plastic.

Coating gives nonplastic materials some characteristics of plastics by applying a surface film of plastic. Fabrics such as chintz may have a plastic coating. Coated wallpaper can be washed, and coated machinery is protected from rust. In the fluidized-bed, or fusion-bond, process, a preheated metal part is dipped into a dry plastic powder. The powder melts and fuses with the metal surface to form a uniform coating. Wood, leather, glass, and other materials can also be plastic-coated.

Plastics and the Environment

Most plastics are not biodegradable; that is, they do not break down over time into simpler substances as do foodstuffs or natural fibers. Some scientists are investigating methods of creating biodegradable plastics that deteriorate, for example, on exposure to sunlight. One of the main problems in this type of research is making certain that the plastics degrade only after they are used and not before.

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The problem also arises of what to do with millions of tons of plastic waste. In response, the plastics industry and environmental groups have encouraged the recycling of plastics and continue to study new methods for plastics recovery. Some plastic objects can be ground up and reprocessed into new products. For example, soft-drink bottles made of polyethylene terephthalate (PET) and high-density polyethylene milk jugs have been refabricated into such products as filler for down jackets and sleeping bags, insulation, strapping materials, and plastic lumber. Many communities have recycling programs that allow consumers to recycle various kinds of plastic products.

The effects of plastics on the environment, however, go beyond the issue of recycling. Plastic-foam processors, for example, have used chemicals called chlorofluorocarbons (CFCs) as foaming agents. There is now considerable evidence that CFCs deplete the atmospheric ozone layer, which protects Earth by blocking out much of the Sun’s ultraviolet radiation. Many countries ended or greatly reduced their use of CFCs in the late 20th century, largely through the Montreal Protocol, an international agreement first signed in 1987. Other foaming agents that do not harm the ozone layer have been introduced.

History

Although inventors John Wesley Hyatt and Leo H. Baekeland are legendary figures in the plastics industry, later innovators, and their inventions, deserve no less credit. Vinyl resins were discovered as early as 1838, but polyvinyl chloride did not become available commercially until nearly a century later. Between 1927 and 1933, Waldo Semon of the B.F. Goodrich Company worked on the plasticization of polyvinyl chloride to make the resin suitable for molding.

Other researchers developed various plastics over the next several decades. The German chemist Otto Röhm had experimented with acrylic resins as early as 1901. In 1931 the Röhm and Haas Company first manufactured acrylics, under the trade name Plexiglas, for use as safety glass. An American chemist, Wallace H. Carothers of the Du Pont Company, headed the group of researchers that discovered nylon in 1935. Nylon was introduced commercially in 1938 and has since found increasing uses as a fiber and a plastic. There are several different types of nylon. In 1937 Otto Bayer of Germany conducted the original research that ultimately led to the production of polyurethanes, which were introduced commercially in 1954.

In 1938 Roy Plunkett of Du Pont was surprised to find a white powder in what had been a cylinder of tetrafluoroethylene gas. This powder, polytetrafluoroethylene (PTFE), has become an important plastic, better known by the Du Pont trade name Teflon. Full-scale commercial production of PTFE began in 1948. Commonly used in nonstick cookware, it also has many other applications.

As early as the 19th century it was known that monomers of styrene, like monomers of vinyl chloride and acrylate, could be polymerized. Large-scale commercial production of polystyrene, however, did not begin until the late 1930s.

From 1940 to 1950 many more important plastic resins were introduced commercially, including unsaturated polyester, low-density polyethylene (LDPE), fluorocarbons, cellulose propionate, epoxy resins, silicones, and acrylonitrile-butadiene-styrene (ABS). High-density polyethylene (HDPE) was first produced in 1957 by Karl Zeigler of West Germany. That same year, the Italian scientist Giulio Natta, using methods similar to those of Zeigler, was able to polymerize propylene and thereby produce polypropylene.

From the 1950s to the 1970s, a number of engineering plastics were developed—plastics that because of their strength and durability are suitable for use in construction, machine parts, aerospace, chemical processing equipment, and other demanding uses. These engineering plastics include polycarbonate, polyacetal, polyphenylene oxide, polyphenylene sulfide, polysulfone, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyetheretherketone (PEEK). The importance of the engineering plastics grew in the 1980s, and newer ones such as liquid crystal polymers continued to be developed.

Starting in the late 20th century, much research focused on plastics alloys and blends and reinforced composite plastics. Alloys and blends are combinations of plastics created to improve plastic materials at lower costs. Such combinations have included polycarbonate and ABS, and PET and PBT. Reinforced composite plastics have been of particular interest because they provide great strength and light weight. Composites have been taking the place of metals in many applications.

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